Ordered mesoporous materials for water pollution treatment:Adsorption and catalysis

To meet the growing emission of water contaminants,the development of new materials that enhance the efficiency of the water treatment system is urgent.Ordered mesoporous materials provide opportunities in environmental processing applications due to their exceptionally high surface areas,large pore sizes,and enough pore volumes.These properties might enhance the performance of materials concerning adsorption/catalysis capability,durability,and stability.In this review,we enumerate the ordered mesoporous materials as adsorbents/catalysts and their modifications in water pollution treatment from the past decade,including heavy metals(Hg^(2+),Pb^(2+),Cd^(2+),Cr^(6+),etc.),toxic anions(nitrate,phosphate,fluoride,etc.),and organic contaminants(organic dyes,antibiotics,etc.).These contributions demonstrate a deep understanding of the synergistic effect between the incorporated framework and homogeneous active centers.Besides,the challenges and perspectives of the future developments of ordered mesoporous materials in wastewater treatment are proposed.This work provides a theoretical basis and complete summary for the application of ordered mesoporous materials in the removal of contaminants from aqueous solutions.

Optimization of a digested sludge-derived mesoporous material as an efficient and stable heterogeneous catalyst for the photo-Fenton reaction

The anaerobic digestion of sludge has recently received increased interest because of the potential to transform organic matter into methane‐rich biogas. However, digested sludge, the residue produced in that process, still contains high levels of heavy metals and other harmful substances that might make traditional disposal difficult. We have devised a facile method of converting digested sludge into a mesoporous material that acts as an effective and stable heterogeneous catalyst for the photo‐Fenton reaction. A comparison of the removal of rhodamine B under different conditions showed that FAS‐1‐350, which was synthesized by mixing the digested sludge with a 1 mol/L（NH4）2Fe（SO4）2 solution followed by calcination at 350 °C, exhibited the best catalytic activity owing to its faster reaction rate and lower degree of Fe leaching. The results indicate that Fe^（2＋）‐loaded catalysts have significant potential to act as stable and efficient heterogeneous promoters for the photo‐Fenton reaction, with better performance than Fe^3＋‐loaded catalysts because the Fe（II）/Fe（III）compounds formed in the calcination process are necessary to sustain the Fenton reaction. This protocol provides an alternative, environmentally friendly method of reusing digested sludge and demonstrates an easily synthesized mesoporous material that effectively degrades azo dyes.

Adsorption behavior of phosphate on Lanthanum(Ⅲ) doped mesoporous silicates material

A series of lanthanum doped meosoporous MCM-41 （LaxM41, x is Si/La molar ratio） was prepared by sol-gel method. The surface structure of the materials was investigated with X-ray diffraction and N2 adsorption/desorption technique. The content of La in the materials was determined by ICE It was found that the La content of La25M41, La50M41 and La100M41 was 7.53%, 3.89% and 2.32%, respectively. The phosphate adsorption capacities increased with increasing amount of La incorporation. With 0.40 g La25M41 99.7% phosphate could be removed. The effects of Si/La molar ratio, LaxM41 dose, pH, initial concentration of phosphate solution, co-ions on phosphate adsorption were also evaluated. The phosphate adsorption kinetics of LaxM41 could be well-described by the pseudo second-order model, and Langmuir isotherm fit equilibrium data much better than the Freundlich isotherm.

Synthesis of Ln-doped MCM-41 mesoporous materials and their catalytic performance in oxidation of styrene

Using cetyl-trimethyl-ammonium bromide （CTMAB） as the template agent and tetraethylorthosilicate （TEOS） as the silica source, the MCM-41 mesoporous materials were synthesized with La or Ce incorporated in the framework under hydrothermal conditions. The structure and the state of La or Ce were investigated through the analyses of XRD, nitrogen adsorption-desorption, FT-IR, and UV-Vis. XRD and N2 adsorption-desorption results showed that Ln-MCM-41 exhibited the loss of the lattice ordering of the MCM-41 construct, and larger unit cell parameter and pore diameter than pure silica MCM-41. The FT-IR and UV-Vis results indicated the presence of isolated tetra-coordinated La or Ce ions in the framework and other Ln species dispersed highly on the Ln-MCM-41 surface simultaneously. Furthermore, their catalytic behaviors in the oxidation of styrene were studied using H2O2 as the oxidant. The La-MCM-41 catalysts exhibited high reactivity and the reactivity increased with the increase of the La content in the La-MCM-41 samples. On the contrary, Ce-MCM-41 catalysts showed low reactivity in the oxidation of styrene and the conversion of styrene decreased with the increase of the Ce content in the Ce-MCM-41 samples.

Study on Hydrothermal Stability and Catalytic Activity of Al-SBA-15 Mesoporous Materials Prepared by Impregnation Method

The mesoporous Al-SBA-15 zeolite was obtained via impregnation of pure silica-based SBA-15 zeolite with aluminum nitrate.The Al-SBA-15 sample was calcined in air at 800 ℃ for 6 h and hydrothermally treated at near 100 ℃ for 120 h,respectively,and then the thermal and hydrothermal stability of Al-SBA-15 sample was investigated by X-ray diffractometry (XRD),scanning electron microscopy (SEM),transmission electron microscopy (TEM) and nitrogen adsorption and desorption techniques.The Al-SBA-15 sample was also studied by 27 Al nuclear magnetic resonance (27 Al NMR) and ammonia temperature programmed desorption (NH 3-TPD) techniques.In addition,the catalytic activity of Al-SBA-15 zeolite was investigated by the Friedel-Crafts reactions of 2,4-di-tert-butylphenol with cinnamyl alcohol.The test results showed that the thermal and hydrothermal stability of Al-SBA-15 zeolite was better than that of SBA-15 zeo-lite.The Al-SBA-15 zeolite sample prepared by impregnation method exhibits more framework aluminum species and Al-O-Si units.Therefore,the number of the surface hydroxyl groups was reduced,resulting in the stabilization of framework structure ofAl-SBA-15 zeolite.The aluminum species can form weak and medium-strong acid sites with catalytic activity.

Structural Evolvement of Heating Treatment of Mg/AI-LDH and Preparation of Mineral Mesoporous Materials

Although hydrotalcite, or layered double hydroxides （LDHs）, is not a common mineral, it is an important material that can be easily synthesized in laboratory. In this study, structural evolvement and BET surface area changes of heat treated Mg/AI-LDH is evaluated by XRD, TEM and N2-BET analyses. The results indicate that the magnesium-aluminum LDH with carbonate as interlayer anion, periclase-like oxides was formed at temperatures of 400-800℃. Meanwhile, 2-3 nanometer mesoporous were formed during decomposition of LDH. However, the heat treated samples still preserve the morphology of the original LDH plates. Periclase-like formed from LDH heat treatment may re-hydrolyze and recover the structure of LDH. However, crystallinity of the recovered LDH is lower than that of the original LDH. This heat treatment will result in formation of （Mg, Al）-oxide nano-crystals and nanopores among the nano-crystals. When heating temperature exceeds 1000, the periclase-like （Mg, Al）-oxide is transformed into a composite with periclase （MgO） and spinel phases. The periclase can be re-hydrolyzed and dissolved in HCl solution. After acid treatment, the sample with a high surface area is composed of spinel nano-crystals and nanopores among them. Our results will provide a new and economic way to synthesize mesoporous materials through pathways of phase transformation of precursor materials with different composition.

SYNTHESIS OF MESOPOROUS POLY(STYRENE-co-MALEIC ANHYDRIDE)/SILICA HYBRID MATERIALS VIA A NONSURFACTANT-TEMPLATED SOL-GEL PROCESS

Mesoporous poly(styrene-co-maleic anhydride)/silica hybrid materials have been prepared. The synthesis was achieved by the HCl-catalyzed sol-gel reactions of tetraethyl orthosilicate (TEOS) and styrene-maleic anhydride copolymer in the presence of 3-aminopropyl triethoxysilane (APTES) as a coupling agent and citric acid as a nonsurfactant template or pore-forming agent, followed by ethanol extraction. Characterization results from nitrogen sorption isotherms and powder X-ray diffraction indicate that polymer-modified mesoporous materials with large specific surface areas (e.g. 900 m(2)/g) and pore volumes (e.g. 0.6 cm(3)/g) could be prepared. As the citric acid concentration is increased, the specific surface areas, pore volumes and pore diameters of the hybrid materials increase.

SYNTHESIS AND BIOTECHNOLOGICAL APPLICATIONS OF VINYL POLYMERINORGANIC HYBRID AND MESOPOROUS MATERIALS

We describe the sol-gel synthesis of a new family of organic-inorganic hybrid materials, in which various vinyl polymers are covalently bonded to and uniformly distributed in inorganic oxide matrices. The materials can be tailored to have both good toughness and hardness while maintaining excellent optical transparency. Doping the sol-gel metal oxides with optically active compounds such as D-glucose results in new optical rotatory composite materials. Removal of the dopant compounds from the composites affords mesoporous oxide materials; which represents a new, nonsurfactant-templated route to mesoporous molecular sieves. We have successfully immobilized a series of enzymes and other bioactive agents in mesoporous materials. Catalytical activities of the enzyme encapsulated in mesoporous materials were found to be much higher than those encapsulated in microporous materials.

Titanium-Containing Mesoporous Materials: Synthesis and Application in Selective Catalytic Oxidation

Titanium-containing mesoporous molecular sieves are of great significance in selective catalytic oxidation processes with bulky molecules. Recent researches and developments on the designing and synthesis of Ti-containing mesoporous materials have been reviewed. Various strategies for the preparation of Ti-containing mesoporous materials, such as direct synthesis and post-synthesis, are described. Modifications of Ti-containing mesoporous materials by surface-grafting and atom-planting are also discussed. All approaches aimed mainly at the improving of the stability, the hydrophobicity, and mostly the catalytic activity. Structural and mechanistic features of various synthetic systems are discussed. Ticontaining mesoporous materials in liquid phase catalytic oxidation of organic compounds with H2O2 as an oxidant is briefly summarized, showing their broad utilities for green synthesis of fine chemicals by catalytic oxidative reactions.

Synthesis of Mesoporous Cu-Mn-Al_2O_3 Materials and Their Applications to Preferential Catalytic Oxidation of CO in a Hydrogen-rich Stream

A series of mesoporous Cu-Mn-Al2O3（CMA） materials was synthesized at moderate temperature and their structures were characterized by XRD, N2 physical adsorption and TPR techniques. It was found that using metal complex ion[Cu（NH3） 4^2＋-Mn（NH3）6^2＋] as raw materials is easier to form good-structure mesoporous Cu-Mn-Al2O3 materials than using its nitrate salt [Cu（NO3）2-Mn（NO3）2]. The TPR tests results indicate that CuO and MnOx were homogeneously dispersed in the mesoporous materials. Their catalytic application to preferential catalytic oxidation of CO in a hydrogen-rich stream was studied. The activity varies in the order of CMA（1：1, molar ratio）〉 CMA（1：2）〉CMA（2：1）〉CMA（CP）〉CMA（1：0）≈CMA（0：1）. The CMA（1：0） and CMA（0：1） have lower activity compared to other samples, implying that there existed coordination effect between Cu-Mn in the samples. The selectivity varied in the order of CMA（0：1）≥CMA（1：2）〉CMA（1：1）〉CMA（2：1）〉CMA（1：0） at higher temperature （≥ 120 ℃）, indicating that increasing the Cu content enhanced the conversion of H2. The sample CMA（CP） made by coprecipitation method has a lower CO oxidation activity and selectivity than its counter-parts of mesoporous Cu-Mn-Al2O3 materials[CMA（1：2）], this attributed to the lower surface area of the former and poor interaction of CuO with MnOx.

Synthesis and Characterization of Worm-shaped Tubular Lanthanum Aluminum Composite Mesoporous Materials

The lanthanum aluminum mesoporous materials were synthesized using sodium dodecyl sulfate as a template agent by ultrasonic hydrothermal method.The resulting samples were characterized by low angle X-ray diffraction（XRD）,N2 adsorption-desorption studies,transmission electron microscopy（TEM）and surface morphology analysis（SEM）,surface acid（NH3-TPD）,reducibility properties（TPR）,X-ray energy dispersive spectrometer（EDS）and thermogravimetric analysis（TG/DTG）.A l/La composite mesoporous material were synthesized with n（Al）︰n（La）=70︰1.0,80°C of reaction temperature,20 h of reaction time,12 h of crystallization time,650°C of calcination temperature.The specific surface area of the sample is 273.90 m 2 ·g ？1 ,with the average diameter 5.642 nm and pore volume 0.2354 cm 3 ·g ？1 .The samples have mesoporous structure and its particles are similar to a worm-shaped tubular structure.The influence of calcination temperature on the surface physical and chemical properties of Al/La composited mesoporous materials was examined,and the results showed that the acid strength was increased but the amount of acidic sites is decreased as the calcination temperature increased.It was found that the sample calcined at 650°C had appropriate acid content,acid strength and better reducibility.

Synthesis and Characterization of Mesoporous Materials MCM-41 Incorporated by Yttrium, Neodymium and Samarium

Using cetyl-trimethyl-ammonium bromide （CTMAB） as template and tetraethylortho-silicate （TEOS） as silica source, the MCM-41 mesoporous materials incorporated in framework by Y, Nd and Sm were synthesized by hydrothermal synthesis method. The structure, morphology of materials and the state of Y, Nd, Sm in materials were investigated by means of XRD, nitrogen adsorption-desorption, SEM, IR spectrometry, TG-DTA. The XRD results indicate that the samples possess the mesoporous MCM-41 structures with ordered hexagonal arrangements. Y, Nd and Sm ions can get into the framework of mesoporous materials. Nitrogen adsorption desorption isotherms show that the samples have typical mesopores characteristics. SEM micrographs reveal that incorporated sampies show a spherical morphology and the diameters are averagely 0. l0 to 0.15 μm. In IR spectrum of samples, there are the feature adsorption peaks about Si-O-Ln（Ln=Y, Sm, Nd）at 960-985 cm^-1, which affirm that Y, Nd, Sm ions locate in the framework of several mesoporous materials. Results from TG-DTA analysis suggest that two different template sorption sites exist in the framework of YMCM-41, SmMCM-41, NdMCM-41, which powerfully proves that the presence of Y, Nd and Sm in Si framework of the materials.

Synthesis and Characterization of Novel Layered Lithium Sodium Silicate (Silinaite) and the Mesoporous Materials from Silinaite

Novel layered silinaite has been synthesized using an aqueous mixture of water glass, LiOH and NaOH under hydrothermal crystallization. Subsequently transformation of silinaite into mesoporous materials （SDM） was achieved at mild condition using cetyltfimethylammonium bromide as structure-directing agents. The resulting samples were characterized by XRD, SEM, FTIR nitrogen adsorption-desorption isotherms and catalytic performance in bulky molecular involved reaction. The results revealed that synthesized mesoporous materials derived from the silinaite exhibited an ordered hexagonal crystal structure with average pore diameter 2.7 nm and BET surface area 817m^2/g. The SDM-supported ZnCl2 catalyst, prepared by impregnationevaporation method, retained the mesoporous structure and showed high selectivity in alkylation of benzene with benzyl chloride.

Gallery-templated Synthesis of Titanium/Silicon-containing Mesoporous Montmorillonite-based Catalytic Materials

A mesoporous titanium/silicon -containing montmorillonite-based catalytic materials has been synthesized by novel gallery-templated techniques. XRD, SEM, framework IR, and N2 adsorptiondesorption isotherms provided evidence of the formation of Si/Ti pillars. The synthetic materials show potential catalytic application for hydroxylation of phenol with peroxide.

Analysis on Band Gaps of MCM-41 Type of Materials

The concept and analysis method of photonic crystals and band gaps are introduced into one-dimensional(1D) ordered mesoporous materials. MCM-41 type of materials are treated theoretically as photonic crystals. The formation of band gaps is exhibited and confirmed by a calculation of transfer matrix technique. PBG was found around 9-42 nm in soft X-ray region. The photonic band-gap was predicted to be dependent on incident direction, pore size and lattice constant. The mesoporous materials with different pore sizes and different lattice constants have different band-gap widths.

Effect of Surfactant/Silica and Hydrothermal Time on the Specific Surface Area of Mesoporous Materials from Coal-Measure Kaolin

Mesoporous materials with the highest surface area were synthesized by hydrothermal treatment from coal-measure kaolin using cetyltrimethylammonium bromide（CTAB）as template.The effect of several factors on surface area of products also had been discussed.The products were characterized by FT- IR,HRTEM and N 2 adsorption and desorption isotherm plot methods.There was typical structure as Si-O,Si- OH and Si-O-Si of mesoporous materials in the framework of synthesized materials;the pore size distributions of the products showed a sharp peak at 3.82 nm.The effect of hydrothermal treatment time and the amount of template on the specific surface area of mesoporous materials was important,when the Surf/Si=0.135,and hydrothermal time=12 h,and the surface area of the product reached up to 1 070 m2/g,which was higher than other products.

Synthesis and Characterization of Mesoporous Materials MCM-41 Incorporated by Yttrium, Neodymium and Samarium

Using cetyl-trimethyl-ammonium bromide （CTMAB） as template agent and tetraethylorthosilicate （TEOS） as silica Source, the MCM-41 mesoporous materials were synthesized with Y, Nd and Sm incorporated in the framework under hydrothermal conditions. The structure and the micro-morphology of the materials and the state of Y, Nd and Sm were investigated through the analyses of XRD, nitrogen adsorption-desorption isotherm, SEM, IR and TG-DTA. The XRD resuits indicate that the synthetic samples are of typical structure of mesoporous MCM-41 with ordered hexagonal arrangements, and Y, Nd and Sm can be incorporated into the framework of these mesoporous materials. Nitrogen adsorption-desorption isotherms show that the samples possess the typical mesopores character. SEM micrographs reveal that the incorporated samples show a well-defined spherical morphology with the diameter ranging 0.10 - 0.15μm. The occurrence of two different template sorption sites in the framework as revealed by TG-DTA analysis further suggests the presence of Y, Nd and Sm in siliceous framework.

Double-Mesopore V-MSU-X Silica and its Pure Siliceous Derivative Prepared by One Synthesis System

Non-ionically templated organo-modified MSU-2 mesoporous silicas have been prepared in neutral medium by co-condensation TEOS and vinyltriexoylsiloxane (VTES) and exhibit highly symmetric bimodal mesopore systems. A bromination reaction of V-MSU-2 provides evidence for attachment of most vinyl groups to the accessible surface within the channels. Further, siliceous MSU-2 materials with double pore size have been obtained from calcination of so-produced organo-modified MSU-2 and demonstrate the immense flexibility of the non-ionic templating system.

Synthesis of the Core-Shell Structure Materials as the Controlled-Release Drug Carrier

We have developed a controlled-release drug carrier. Smartly controlled-release polymer nanoparticles were firstly synthesized through RAFT polymerization as the controlled-release core. The structural and particle properties of polymer nanoparticles were characterized by nuclear magnetic resonance spectroscopy (1H-NMR), scanning electron microscope (SEM) and X-ray spectroscopy (EDX). Mesoporous materials were selected as the shell materials to encapsulate the smart core as the stable shell. The mesoporous shell was characterized by transmission electron microscopy (TEM) and scanning electron microscope (SEM). All the results showed that a well-defined core-shell structure with mesoporous structure was obtained, and this controllable delivery system will have the great potential in nanomedicine.

One-pot synthesis of ordered mesoporous Cu-KIT-6 and its improved catalytic behavior for the epoxidation of styrene:Effects of the pH value of the initial gel

The heterogeneously copper-catalyzed oxidative cleavage of styrene was studied using copper-doped mesoporous KIT-6（CU-KIT-6_x） prepared via pH adjustment（where x is the pH：1.43,2.27,3.78,3.97,4.24 or 6.62）.Variations in the catalyst structure and morphology with pH values were characterized by X-ray power diffraction,nitrogen adsorption-desorption analysis,transmission electron microscopy and X-ray photoelectron spectroscopy.As the pH value applied during the initial synthesis,the resulting Cu-KIT-6_x exhibited different structural,textural and surface characteristics,especially in terms of specific copper species and copper content At a pH value of 3.78,approximately 4.6 wt%copper（Ⅱ） was successfully incorporated into the framework of the initial KIT-6,in the form of-Cu-O-Si- groups.The catalytic performance of each catalyst was evaluated by following the epoxidation of styrene,employing tert-butyl hydroperoxide as the oxidant and CH_3CN as the solvent.A significant styrene conversion of 43.5%with 86.6%selectivity for the desired styrene epoxide was obtained over the Cu-KIT-63.78.A higher Cu content,an ordered cubic laid mesoporous architecture and various specific textural characteristics all combined to endow the Cu-KIT-63.78 with high catalytic activity and good stability.